EP1225179B1 - Catalyseurs de polymerisation d'olefines - Google Patents

Catalyseurs de polymerisation d'olefines Download PDF

Info

Publication number
EP1225179B1
EP1225179B1 EP01500020A EP01500020A EP1225179B1 EP 1225179 B1 EP1225179 B1 EP 1225179B1 EP 01500020 A EP01500020 A EP 01500020A EP 01500020 A EP01500020 A EP 01500020A EP 1225179 B1 EP1225179 B1 EP 1225179B1
Authority
EP
European Patent Office
Prior art keywords
group
cyclopentadienyl
sir
compound
optionally
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP01500020A
Other languages
German (de)
English (en)
Other versions
EP1225179A1 (fr
Inventor
Pascual Royo Gracia
Jesus Cano Sierra
Miguel Angel Flores De Paco
Begona Pena Garcia
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Repsol Quimica SA
Original Assignee
Repsol Quimica SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to PT01500020T priority Critical patent/PT1225179E/pt
Application filed by Repsol Quimica SA filed Critical Repsol Quimica SA
Priority to EP01500020A priority patent/EP1225179B1/fr
Priority to DE60102789T priority patent/DE60102789T2/de
Priority to AT01500020T priority patent/ATE264335T1/de
Priority to ES01500020T priority patent/ES2217104T3/es
Priority to NO20020251A priority patent/NO20020251L/no
Priority to JP2002010510A priority patent/JP3975085B2/ja
Priority to US10/052,476 priority patent/US6753436B2/en
Publication of EP1225179A1 publication Critical patent/EP1225179A1/fr
Application granted granted Critical
Publication of EP1225179B1 publication Critical patent/EP1225179B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F17/00—Metallocenes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65908—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S526/943—Polymerization with metallocene catalysts

Definitions

  • the present invention concerns new organometallic compounds and polymerization catalysts comprising the organometallic compounds.
  • One of the first methods used for achieving a better control of the catalyst properties is the use of a bridge which renders two cyclopentadienyl ligands stereorigid. In this way, it has been possible to obtain highly isotactic and highly syndiotactic propylene polymers.
  • EP 416 815 discloses monocyclopentadienyl catalysts wherein a cyclopentadienyl ligand and an amido ligand are connected through a covalent bridge.
  • the resulting catalyst can incorporate very efficiently long chain alpha-olefins.
  • EP-A-485 821 describes metallocenes of formula (I) characterized by the fact that the transition metal (M') is bonded to only two anionic ligands.
  • organometallic compounds wherein a transition metal is bonded to three ligands which are rigidly connected through structural bridges, wherein at least one ligand is of the cyclopentadienyl type or is isolobal to cyclopentadienyl and the remainder(s) are monovalent anionic ligands.
  • These complexes are effective catalysts for olefin polymerization.
  • By varying the type of ligands and the structure of the two (or three) covalent bridges it is possible to modify the characteristics of the resulting catalyst in terms of molecular weight, comonomer incorporation and tacticity of the obtained polymer.
  • organometallic catalysts of the invention are represented by general formula (I): wherein:
  • a preferred class of compounds belonging to formula Ia is defined by the following formula II: wherein Cp is a cyclopentadienyl or indenyl ring, optionally substituted by one or more R 1 groups, M is selected from Ti, Zr and Hf each R is independently selected from CR 1 2 , SiR 1 2 , CR 1 2 -CR 1 2 , CR 1 2 -SiR 1 2 , SiR 1 2 -SiR 1 2 , wherein R 1 is hydrogen, C 1 -C 20 alkyl, C 3 -C 20 cycloalkyl, C 6 -C 20 aryl, C 3 -C 20 alkenyl, optionally comprising 1 to 5 heteroatoms such as Si, N, P, O, F, Cl, Br.
  • Two groups R' bonded to the same or to adjacent atoms can unite to form a ring.
  • L 2 and L 3 are independently selected from the group consisting of NR 1 , PR 1 , BR 1 , O and S;
  • X is independently selected from the group consisting of hydrogen, halogen, NR 2 , R 2 with R 2 equal to C 1 -C 20 alkyl, C 3 -C 20 cycloalkyl, C 6 -C 20 aryl, C 3 -C 20 alkenyl, optionally comprising 1 to 5 heteroatoms such as Si, N, P, O, F, Cl, Br.
  • D is a neutral Lewis base; preferably it is selected from the group consisting of linear or cyclic ethers, amines and phosphines; most preferably it is selected from the group consisting of diethyl ether, tetrahydrofurane, aniline, dimethylaniline, triphenylphosphine, n-butylamine; p is a number whose value is: 0, 1, 2 or 3.
  • the compounds of formula I are preferably obtained by reacting a compound of formula MX q+3 wherein M is a transition metal of groups 3, 4-10, lanthanide or actinide of the periodic table of the elements, X is a monovalent anionic ligand, preferably selected from the group consisting of N(CH 3 ) 2 , benzyl, and q is 0, 1, 2, 3 depcnding on the valence of M, with a compound of formula III wherein L 1 is a group of the cyclopentadienyl type or is isolobal to cyclopentadienyl, preferably a cyclopentadienyl, indenyl or fluorenyl ring, cyclopenteno[b]tiophenyl cyclopenteno[b:b']-dithiophenyl cyclopenteno[b]pyrrolyl, boratabenzene, phospholyl, dihydroindeno[b]in
  • the intermediate IV is then further reacted with a compound of formula II with X equal to benzyl, to produce the compound of formula I.
  • Another suitable process for the preparation of compounds of formula I is to treat the compound (III) with NR 3 in the presence of MX q+3 .
  • the organometallic compounds of the present invention are useful as catalyst components for polymerizing olefins, preferably alpha-olefins in combination with a co-catalyst.
  • co-catalysts are: aluminoxanes (methylaluminoxane (MAO), modified methylaluminoxane (MMAO), etc.), combinations of alkylaluminiums (such as trimethylaluminium, triethylaluminium, tributylaluminium, etc.) and boron Lewis acids (such as trifluoroborane, tris-pentafluorophenylborane, tris[3,5-bis(trifluoromethyl)phenyl]borane, etc.), and compounds of formula J + K - wherein J + is able to react irreversibly with a group X in formula I and K - is an anion which is able to stabilize the catalytic species which originates from the
  • the catalyst component of the present invention i.e. organometallic compound complex of formula I
  • organometallic compound complex of formula I can be used either as homogeneous catalyst or heterogeneous.
  • organometallic compound (I) wherein at least one L group (selected from L 1 , L 2 and L 3 ) and/or one R group contains a functional group capable or forming a covalent bond with the support.
  • Suitable functional groups are: -O-SiR 2 3 . -SiR 2 nX 3-n , SiR 2 n (OR 2 ) 3-n , -OH.
  • the preferred functional group is -O-SiR 2 3 and is preferably linked to the organometallic compound through a divalent radical comprising from 1 to 20 carbon atoms and from 0 to 5 chain atoms different from carbon and preferably selected from silicon, oxygen, sulfur, boron, phosphorus, nitrogen.
  • the divalent radical joins the group -O-SiR 2 3 either to the Cp ring or to one of the atoms of R or to the anionic ligand, as described in EP 839 836.
  • any type of inorganic oxides are used, for example inorganic oxides such as: silica, alumina, silica-alumina, aluminum phosphates and mixtures thereof, obtaining supported catalysts with contents in transition metals between 0.01 and 4% by weight, preferably between 0.1 and 1%.
  • a particularly preferred support is silica calcined at a temperature between 600°C and 800°C and also MAO modified silica.
  • the cocatalyst is mixed with a solution of a organometallic compound of formula I and a supplementary quantity of it optionally is added to the solution; or the catalyst can directly be added to the polymerization medium, which contains the cocatalyst.
  • the cocatalyst is previously mixed with the supported solid catalyst or it is added to the polymerization medium before the supported catalyst, or both operations are sequentially realized.
  • the most proper polymerization procedure can change according to the chosen type of polymerization process (solution, suspension, slurry or gas phase).
  • the process consists in putting in contact the monomer, or, in certain cases, the monomer and the comonomer, with a catalytic composition according to the present invention, that includes at least one organometallic compound of formulas I and/or II, at a proper temperature and pressure.
  • C 2 -C 12 alpha-olefms such as ethylene, propylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, styrene, divinylbenzene are used as monomer.
  • ethylene is used as monomer, it can be either homopolymerized, or copolymerized in the presence of at least one comonomer selected from propylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene.
  • comonomers are used in proportions from 0.1 to 70% by weight of the total of the monomers.
  • the density of polymers ranges between 0.950 and 0.970 kg/cm 3 in the case of copolymerization of ethylene the density is as low as 0.880 kg/cm 3 .
  • the used temperature will be between 30° and 110 °C, the same which is typically used in gas phase, while for the solution process the usual temperature will be between 120° and 250°C.
  • Preferred compounds of formula I are:
  • Further examples include compounds wherein the zirconium atom in the previous examples shown in g) is replaced by Ti, Hf.
  • Further examples include compounds wherein the zirconium atom in the previous examples shown in h) is replaced by Ti, Hf.
  • the reactor is kept under stirring and thermostated at 70 °C. After 1h, the polymerization was stopped by addition of acidified methanol. 1.81 g of polyethylene were obtained.
  • Example 2 was repeated but using 12.9 ml of MAO aand 4.2 micromoles of compound 5. After 30' of polymerization 2.78 g of polyemer were obtained.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)

Claims (11)

  1. Composant de catalyseur de polymérisation d'oléfines comprenant un composé organométallique de formule générale I
    Figure 00480001
    dans laquelle :
    M est un métal de transition des groupes 3, 4 à 10, un lanthanide ou un actinide du tableau périodique des éléments, de préférence le titane, le zirconium ou l'hafnium ;
    chaque R est indépendamment un pont structurel qui connecte de façon rigide deux ligands L1, L2 et L3 et est formé de 1 à 4 atomes en chaíne choisis parmi le carbone, le silicium, le germanium, l'oxygène, le bore ;
    m, n et o valent 0 ou 1, à condition que m+n+o vaille 2 ou 3 ;
    L1 est un ligand de type cyclopentadiényle ou est isolobal par rapport au cyclopentadiényle, de préférence un cycle cyclopentadiényle, indényle ou fluorényle, cyclopentène[b]pyrrolyle, cyclopentène[b:b1]dithiophényle, cyclopentène[b]thiophényle, boratabenzène, phospholyle, dihydro-indéno[b]indolyle, éventuellement substitué par un ou plusieurs groupes R1 ; dans le cas préféré entre tous, un cycle cyclopentadiényle, indényle ou fluorényle, éventuellement substitué par un ou plusieurs groupes R1
    L2 est un ligand de type cyclopentadiényle ou est isolobal par rapport au cyclopentadiényle ou un ligand anionique monovalent choisi dans le groupe formé par les atomes N, P, B, lorsque m+n = 2, et choisi dans le groupe formé par NR1, PR1, BR1, les atomes O et S lorsque m+n = 1 ;
    L3 est un ligand anionique monovalent choisi dans le groupe formé par les atomes N, P, B, lorsque n+o = 2, et choisi dans le groupe formé par NR1, PR1, BR1, les atomes O et S lorsque n+o = 1 ;
    R1 est un atome d'hydrogène, un radical alkyle en C1-C20, un radical cycloalkyle en C3-C20, un radical aryle en C6-C20, un radical alcényle en C3-C20, comprenant éventuellement 1 à 5 hétéroatomes tels que les atomes Si, N, P, O, F, Cl, Br ;
    chaque X est choisi indépendamment dans le groupe formé par l'atome d'hydrogène, les halogènes, NR2 2, R2 où R2 équivaut à un radical alkyle en C1-C20, un radical cycloalkyle en C3-C20, un radical aryle en C6-C20, un radical alcényle en C3-C20, comprenant éventuellement 1 à 5 hétéroatomes tels que les atomes Si, N, P, O, F, Cl, Br ;
    q est un nombre ayant pour valeur : 0, 1, 2 ou 3, selon la valence du métal M ;
    D est une base neutre de Lewis,
    p est un nombre ayant pour valeur : 0, 1, 2 ou 3.
  2. Composant de catalyseur selon la revendication 1 dans lequel n vaut 0 et chaque R est choisi indépendamment parmi CR1 2, SiR2 1, CR1 2-CR1 2, CR1 2-SiR2 1,
    SiR2 1-SiR2 1 ; dans laquelle R1 est choisi indépendamment parmi un atome d'hydrogène, un radical alkyle en C1-C20, un radical cycloalkyle en C3-C20, un radical aryle en C6-C20, un radical alcényle en C3-C20, comprenant éventuellement 1 à 5 hétéroatomes tels que les atomes Si, N, P, O, F, Cl, Br .
  3. Composant de catalyseur selon la revendication 1 dans lequel D est choisi dans le groupe formé par les éthers linéaires ou cycliques, les amines et les phosphines.
  4. Composant de catalyseur selon la revendication 1 dans lequel le composé organométallique possède la formule (II)
    Figure 00500001
    dans laquelle Cp est cycle cyclopentadiényle ou indényle, éventuellement substitué par un ou plusieurs groupes R1, M est choisi parmi les atomes Ti, Zr et Hf
    chaque R est choisi indépendamment parmi CR1 2, SiR2 1, CR1 2-CR1 2, CR1 2-SiR2 1 SiR2 1-SiR2 1, dans laquelle R1 est un atome d'hydrogène, un radical alkyle en C1-C20, un radical cycloalkyle en C3-C20, un radical aryle en C6-C20, un radical alcényle en C3-C20, comprenant éventuellement 1 à 5 hétéroatomes tels que les atomes Si, N, P, O, F, Cl, Br ;
    L2 et L3 sont choisis indépendamment dans le groupe formé par NR1, PR1, BR1, les atomes O et S ;
    X est choisi indépendamment dans le groupe formé par l'atome d'hydrogène, les halogènes, NR2, R2 où R2 équivaut à un radical alkyle en C1-C20, un radical cycloalkyle en C3-C20, un radical aryle en C6-C20, un radical alcényle en C3-C20, comprenant éventuellement 1 à 5 hétéroatomes tels que les atomes Si, N, P, O, F, Cl, Br ;
    D est une base neutre de Lewis ;
    p est un nombre ayant pour valeur : 0, 1, 2 ou 3.
  5. Composant de catalyseur selon la revendication 1 dans lequel o est égal à 0.
  6. Composant de catalyseur selon la revendication 1 dans lequel au moins un groupe L choisi parmi L1, L2 et L3 et/ou un groupe R, contiennent un groupe -O-SiR2 3
  7. Composant de catalyseur comprenant un composé selon les revendications 1-6 et un support poreux
  8. Composant de catalyseur de polymérisation d'oléfines comprenant un composant de catalyseur selon les revendications 1-7 et un co-catalyseur choisi parmi les aluminoxanes et les acides de Lewis du bore.
  9. Procédé pour la préparation des composants de catalyseur selon les revendications 1-6 comprenant l'étape de faire réagir un composé de formule MXq+3, dans laquelle M est un métal de transition des groupes 3, 4-10, un lanthanide ou un actinide du tableau périodique des éléments. X est un ligand anionique monovalent et q vaut 0, 1, 2 ou 3 selon la valence du métal M, avec un composé de formule III
    Figure 00510001
    dans laquelle
    chaque R est indépendamment un pont structurel qui connecte de façon rigide L1, L2 et L3 et est formé de 1 à 4 atomes en chaíne choisis parmi les atomes de carbone, de silicium, de germanium, d'oxygène, de bore ; ces atomes peuvent faire partie de cycles condensés, de cycles aromatiques ou de cycles spiro ;
    m, n et o valent 0 ou 1, à condition que m+n+o vaille 2 ou 3 ;
    L1 est un groupe de type cyclopentadiényle ou est isolobal par rapport au cyclopentadiényle, éventuellement substitué par un ou plusieurs groupes R1 ;
    L2 est un groupe de type cyclopentadiényle ou est isolobal par rapport au cyclopentadiényle, ou est choisi dans le groupe formé par les atomes N, P, B, lorsque m+n = 2, et choisi dans le groupe formé par NR1, PR1, BR1, les atomes O et S lorsque m+n = 1 ;
    L3 est choisi dans le groupe formé par les atomes N, P, B, lorsque n+o = 2, et choisi dans le groupe formé par NR1, PR1, BR1, les atomes O et S lorsque n+o = 1 ; et
    R1 est un atome d'hydrogène, un radical alkyle en C1-C20, un radical cycloalkyle en C3-C20, un radical aryle en C6-C20, un radical alcényle en C3-C20, comprenant éventuellement 1 à 5 hétéroatomes tels que les atomes Si, N, P, O, F, Cl ou Br.
  10. Procédé pour la polymérisation d'oléfines caractérisé par l'utilisation d'un catalyseur selon la revendication 8.
  11. Composé pouvant s'obtenir en faisant réagir une mole d'un composé de formule (III) avec trois moles d'une base forte choisie dans le groupe formé par le butyllithium, NaH et KH, dans laquelle ledit composé de formule (III) est
    Figure 00520001
    dans laquelle
    chaque R est indépendamment un pont structurel qui connecte de façon rigide L1, L2 et L3 et est formé de 1 à 4 atomes en chaíne choisis parmi les atomes de carbone, de silicium, de germanium, d'oxygène, de bore ; ces atomes peuvent faire partie de cycles condensés, de cycles aromatiques, ou de cycles spiro
    m, n et o valent 0 ou 1, à condition que m+n+o vaille 2 ou 3 ;
    L1 est un groupe de type cyclopentadiényle ou est isolobal par rapport au cyclopentadiényle, éventuellement substitué par un ou plusieurs groupes R1
    L2 est un ligand de type cyclopentadiényle ou est isolobal par rapport au cyclopentadiényle, ou est choisi dans le groupe formé par les atomes N, P, B, lorsque m+n = 2, et choisi dans le groupe formé par NR1, PR1, BR1, les atomes O et S lorsque m+n = 1 ;
    L3 est choisi dans le groupe formé par les atomes N, P, B, lorsque n+o = 2, et choisi dans le groupe formé par NR1, PR1, BR1, les atomes O et S lorsque n+o = 1 ; et R1 est un atome d'hydrogène, un radical alkyle en C1-C20, un radical cycloalkyle en C3-C20, un radical aryle en C6-C20, un radical alcényle en C3-C20, comprenant éventuellement 1 à 5 hétéroatomes tels que les atomes Si, N, P, O, F, Cl, Br.
EP01500020A 2001-01-18 2001-01-18 Catalyseurs de polymerisation d'olefines Expired - Lifetime EP1225179B1 (fr)

Priority Applications (8)

Application Number Priority Date Filing Date Title
EP01500020A EP1225179B1 (fr) 2001-01-18 2001-01-18 Catalyseurs de polymerisation d'olefines
DE60102789T DE60102789T2 (de) 2001-01-18 2001-01-18 Olefinpolymerisationskatalysatoren
AT01500020T ATE264335T1 (de) 2001-01-18 2001-01-18 Olefinpolymerisationskatalysatoren
ES01500020T ES2217104T3 (es) 2001-01-18 2001-01-18 Catalizadores de la polimerizacion de olefinas.
PT01500020T PT1225179E (pt) 2001-01-18 2001-01-18 Catalisadores de polimerizacao de olefinas
NO20020251A NO20020251L (no) 2001-01-18 2002-01-17 Katalysator for olefinpolymerisering
US10/052,476 US6753436B2 (en) 2001-01-18 2002-01-18 Olefin polymerization catalysts
JP2002010510A JP3975085B2 (ja) 2001-01-18 2002-01-18 オレフィン重合触媒

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP01500020A EP1225179B1 (fr) 2001-01-18 2001-01-18 Catalyseurs de polymerisation d'olefines

Publications (2)

Publication Number Publication Date
EP1225179A1 EP1225179A1 (fr) 2002-07-24
EP1225179B1 true EP1225179B1 (fr) 2004-04-14

Family

ID=8183459

Family Applications (1)

Application Number Title Priority Date Filing Date
EP01500020A Expired - Lifetime EP1225179B1 (fr) 2001-01-18 2001-01-18 Catalyseurs de polymerisation d'olefines

Country Status (8)

Country Link
US (1) US6753436B2 (fr)
EP (1) EP1225179B1 (fr)
JP (1) JP3975085B2 (fr)
AT (1) ATE264335T1 (fr)
DE (1) DE60102789T2 (fr)
ES (1) ES2217104T3 (fr)
NO (1) NO20020251L (fr)
PT (1) PT1225179E (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0856524A1 (fr) * 1997-02-01 1998-08-05 Repsol Quimica S.A. Composants catalytiques hétérogènes pour la polymérisation des oléfines, procédé pour leur préparation et leur utilisation
US10465289B2 (en) * 2016-12-30 2019-11-05 L'Air Liquide, Société Anonyme pour l'Etude at l'Exploitation des Procédés Georges Claude Zirconium, hafnium, titanium precursors and deposition of group 4 containing films using the same
CN110922424A (zh) * 2018-09-20 2020-03-27 中国石油天然气股份有限公司 [p,p]型全杂环非茂金属催化剂及其制备方法与应用
CN110938088A (zh) * 2018-09-21 2020-03-31 中国石油天然气股份有限公司 [n,p]型全杂环非茂金属催化剂及其制备方法与应用

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3718888A1 (de) 1987-06-05 1988-12-22 Hoechst Ag Verfahren zur herstellung eines 1-olefinpolymers
NZ235032A (en) 1989-08-31 1993-04-28 Dow Chemical Co Constrained geometry complexes of titanium, zirconium or hafnium comprising a substituted cyclopentadiene ligand; use as olefin polymerisation catalyst component
DE59107926D1 (de) * 1990-11-12 1996-07-18 Hoechst Ag Metallocene mit Liganden aus 2-substituierten Indenylderivaten, Verfahren zu ihrer Herstellung und ihre Verwendung als Katalysatoren
ES2120868B1 (es) 1995-08-03 2000-09-16 Repsol Quimica Sa Sistema de catalizadores hetereogeneos tipo metalogeno, para procesos de obtencion de poliolefinas.
US6635778B1 (en) 1996-10-30 2003-10-21 Repsol Quimica S.A. Catalysts systems for the polymerization and copolymerization of alpha-olefins
DE69703728T2 (de) 1996-10-31 2001-06-28 Repsol Quimica S.A., Madrid Katalysatorsysteme für die Polymerisation und Copolymerisation von Alpha-Olefinen
KR100380018B1 (ko) 1998-04-09 2003-10-04 주식회사 엘지화학 메탈로센담지촉매및이를이용한올레핀중합방법
EP0953581B1 (fr) 1998-04-27 2004-01-07 Repsol Quimica S.A. Sytèmes catalytiques pour la polymérisation et la copolymérisation d'alpha-oléfines
EP0953580B1 (fr) 1998-04-29 2004-04-14 Repsol Quimica S.A. Préparation et utilisation de composés catalytiques hétérogènes pour la polymérisation d'oléfines
JP2001122886A (ja) 1999-10-26 2001-05-08 Repsol Quimica Sa 単一の炭素架橋したビスシクロペンタジエニル化合物及びこれのメタロセン錯体

Also Published As

Publication number Publication date
EP1225179A1 (fr) 2002-07-24
PT1225179E (pt) 2004-08-31
NO20020251D0 (no) 2002-01-17
ATE264335T1 (de) 2004-04-15
JP2002308924A (ja) 2002-10-23
DE60102789D1 (de) 2004-05-19
US20020115560A1 (en) 2002-08-22
ES2217104T3 (es) 2004-11-01
DE60102789T2 (de) 2005-05-12
NO20020251L (no) 2002-07-19
JP3975085B2 (ja) 2007-09-12
US6753436B2 (en) 2004-06-22

Similar Documents

Publication Publication Date Title
US6943225B2 (en) Multinuclear metallocene catalyst
EP2559710B1 (fr) Composition catalytique pour polymérisation une oléfine et procédé de préparation d'une polyoléfine utilisant cette composition
US6858558B2 (en) Olefin polymerization catalyst component and catalyst system and polymerization process using such a catalyst system
KR20010024020A (ko) 2-금속 착체 및 이로부터 제조된 중합 촉매
EP2559711B1 (fr) Catalyseur supporté pour polymériser une oléfine et procédé pour préparer une polyoléfine utilisant ce catalyseur
KR101760494B1 (ko) 메탈로센 담지 촉매 및 이를 이용하는 폴리올레핀의 제조방법
US6534665B1 (en) Single-carbon bridges bys cyclopentadienyl compounds and metallocene complexes thereof
JP3779759B2 (ja) メタロセン化合物及び触媒成分としてのその使用
US6313331B1 (en) Carbene transition metal catalysts
US6831187B2 (en) Multimetallic catalyst compositions for the polymerization of olefins
EP3715382B1 (fr) Catalyseur métallocène supporté et procédé de préparation de polypropylène faisant appel à celui-ci
KR101617871B1 (ko) 이핵 메탈로센 화합물, 촉매 조성물 및 이를 이용한 폴리올레핀의 제조방법
EP1225179B1 (fr) Catalyseurs de polymerisation d'olefines
JP2022517077A (ja) 遷移金属化合物、触媒組成物およびそれを用いたポリプロピレンの製造方法
KR0151873B1 (ko) 메탈로센 화합물, 이의 제조방법 및 이를 촉매로 이용한 고분자의 제조방법
KR101601935B1 (ko) 이핵 메탈로센 화합물, 촉매 조성물 및 이를 이용한 폴리올레핀의 제조방법
US20030166454A1 (en) Heterocyclic-amide catalyst compositions for the polymerization of olefins
KR101229076B1 (ko) 전이 금속 촉매 조성물 및 이를 이용한 폴리 올레핀의 제조 방법
KR101785705B1 (ko) 촉매 조성물 및 이를 이용한 폴리올레핀의 제조방법
KR100205737B1 (ko) 폴리올레핀계 고분자 제조용 촉매로서 유용한 두금속메탈로센화합물
KR100567100B1 (ko) 폴리에틸렌 제조용 균일활성종 촉매, 이의 제조방법 및이를 이용한 중합방법
KR20200139512A (ko) 올레핀 중합용 담지 촉매의 제조방법, 올레핀 중합용 담지 촉매 및 이를 이용하는 폴리올레핀의 제조방법
JP2024500603A (ja) 金属－リガンド錯体、これを含むエチレン系重合体製造用の触媒組成物およびこれを用いたエチレン系重合体の製造方法
KR20200139513A (ko) 올레핀 중합용 담지촉매, 이의 제조방법 및 이를 이용하는 폴리올레핀의 제조방법
KR20220064497A (ko) 혼성 촉매 조성물, 이를 포함하는 촉매 및 이들의 제조방법

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE TR

AX Request for extension of the european patent

Free format text: AL;LT;LV;MK;RO;SI

17P Request for examination filed

Effective date: 20021204

17Q First examination report despatched

Effective date: 20030203

AKX Designation fees paid

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE TR

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE TR

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20040414

Ref country code: CH

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20040414

Ref country code: LI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20040414

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REF Corresponds to:

Ref document number: 60102789

Country of ref document: DE

Date of ref document: 20040519

Kind code of ref document: P

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20040714

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20040714

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20040714

REG Reference to a national code

Ref country code: PT

Ref legal event code: SC4A

Free format text: AVAILABILITY OF NATIONAL TRANSLATION

Effective date: 20040707

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2217104

Country of ref document: ES

Kind code of ref document: T3

ET Fr: translation filed
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20050118

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20050118

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20050118

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20050131

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20050117

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20061218

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: PT

Payment date: 20070119

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 20070123

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20070124

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20070125

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: AT

Payment date: 20070126

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FI

Payment date: 20070129

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 20070320

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20070611

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20070125

Year of fee payment: 7

BERE Be: lapsed

Owner name: S.A. *REPSOL QUIMICA

Effective date: 20080131

REG Reference to a national code

Ref country code: PT

Ref legal event code: MM4A

Free format text: LAPSE DUE TO NON-PAYMENT OF FEES

Effective date: 20080718

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20080118

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 20080801

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20080718

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20080801

Ref country code: FI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20080118

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20080801

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20080118

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20081029

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20080118

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20080131

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20080119

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20080131

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20080119

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20080118